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The synthesis and reactivity of novel perfluorinated phthalonitriles and phthalocyanines.

机译：新型全氟邻苯二甲腈和酞菁的合成与反应性。

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摘要

In this project we have designed bioinspired catalysts modeled after the reactivity of the heme-metalloprotein Cytochrome P450, an enzyme that performs oxidations of hydrocarbons. Our synthetic targets are a novel class of molecules, three-dimensional perfluorinated phthalocyanines. The three-dimensionality is the result of placing bulky substituents, perfluoroisopropyl groups, on the peripheral rings of the phthalocyanines. These models contain no carbon hydrogen bonds, only non-oxidizable carbon fluorines bonds; hence the robustness of these molecules viewed as molecular reactors. First we prepared non-planar perfluorinated phthalonitriles as the ligand precursors. From 19F NMR studies we were able to determine their conformation in solution as being identical to their conformation in solid-state.; The bulky substituents create a fluorine-lined cavity around the metal center while hindering the formation of oxo-bridged dinuclear complexes and minimizing self-aggregation in solution. Activation of oxygen was studied along two lines.; Diamagnetic phthalocyanines may be used for “photodynamic therapy” (PDT), a process in which a light activated sensitizer produces singlet oxygen to cause destruction of tumor cells. Perfluorinated zinc phthalocyanine was synthesized and studied as potential PDT sensitizer. Unlike planar zinc phthalocyanines, our three-dimensional zinc complex does not aggregate, exhibits a long triplet-state lifetime, and produces effectively singlet oxygen, as demonstrated by the photoproduction of L-tryptophan hydroperoxide and the curing of breast tumors in mice.; A three-dimensional perfluorinated cobalt (II) phthalocyanine performs the direct formation of ylidic carbon-phosphorous bonds, a process in which two hydrogen atoms are eliminated as water. This reaction, which occurs at ambient conditions and uses air as the oxidizing agent, eliminates the need for halogenated intermediates. Furthermore, based upon this chemistry, we demonstrate a catalytic cycle illustrating a strategy for transforming a stoichiometric process into a catalytic, environmentally benign, one.
机译：在这个项目中，我们设计了仿照血红素金属细胞色素P 450 （一种执行碳氢化合物氧化的酶）的反应性的生物启发型催化剂。我们的合成靶标是一类新型的分子，即三维全氟酞菁。三维是在酞菁的外围环上放置庞大的取代基全氟异丙基的结果。这些模型不包含碳氢键，仅包含不可氧化的碳氟键；因此，这些分子的坚固性被视为分子反应器。首先，我们制备了非平面全氟化邻苯二甲腈作为配体前体。从 19 NMR研究中，我们可以确定它们在溶液中的构象与它们在固态的构象相同。庞大的取代基在金属中心周围形成了一个衬有氟的空腔，同时阻碍了氧桥联双核络合物的形成，并使溶液中的自聚集最小化。氧气的活化作用沿两条路线进行了研究。抗磁性酞菁可用于“光动力疗法”（PDT），其中光活化敏化剂产生单线态氧以引起肿瘤细胞破坏。合成了全氟酞菁锌并对其进行了研究，以作为潜在的PDT敏化剂。与平面锌酞菁锌不同，我们的三维锌络合物不会聚集，具有长的三重态寿命，并且可以有效产生单线态氧，这可以通过光产生L-色氨酸氢过氧化物和治愈小鼠乳腺肿瘤来证明。三维全氟化钴（II）酞菁可直接形成ylidic碳-磷键，该过程中两个氢原子作为水被消除。该反应在环境条件下发生，并使用空气作为氧化剂，因此无需卤化中间体。此外，基于该化学，我们证明了催化循环，该催化循环说明了将化学计量过程转变成对环境有益的催化过程的策略。

著录项

  • 作者

    Bench, Barbara Anne.;

  • 作者单位

    Brown University.;

  • 授予单位 Brown University.;
  • 学科 Chemistry Inorganic.
  • 学位 Ph.D.
  • 年度 2001
  • 页码 318 p.
  • 总页数 318
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 无机化学;
  • 关键词

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